KR20190099279A - Imprinting device - Google Patents

Abstract

The imprinting device includes a silicon master having a plurality of defined nanofeatures. The anti-stick layer coats the silicon master, wherein the anti-stick layer includes molecules having cyclosiloxanes having at least one silane functional group. The method comprises depositing a formulation on a silicon master comprising a plurality of defined nanofeatures, wherein the formulation comprises a solvent and a molecule having a cyclosiloxane having at least one silane functional group; And forming a master mold by forming an anti-stick layer on the silicon master by curing the formulation, wherein the anti-stick layer comprises molecules. The method includes depositing a silicon based work stamp material on the anti-stick layer of the master mold; Curing the silicone-based work stamp material to form a work stamp comprising a plurality of nanofeatures negative copies; And releasing the work stamp from the master mold.

Description

Imprinting device

Cross Reference to Related Application

This application claims the benefit of US Provisional Application No. 62 / 438,237, filed December 22, 2016, which is incorporated herein by reference in its entirety.

Nano-imprinting technology enables the economical and effective production of nanostructures. Nano-embossing lithography uses an etching process that transfers the nanostructures from the stamp to the substrate following direct mechanical deformation of the resist material by the nanostructured stamp.

Flow cells are devices that allow fluid to flow through passages or wells within a substrate. Patterned flow cells useful in nucleic acid analysis methods include discrete wells of active surface within insertion gap regions. Such patterned flow cells can be useful in biological arrays.

Biological arrays are among the various tools used to detect and analyze molecules including deoxyribonucleic acid (DNA) and ribonucleic acid (RNA). In these applications, arrays are engineered to include probes for nucleotide sequences present in genes in humans and other organisms. In certain applications, for example, individual DNA and RNA probes may be attached at small locations in the geometric grid (or randomly) on an array support. For example, test samples from known humans or organisms can be exposed to the grid so that the complementary fragments hybridize to the probe at individual sites within the array. The array can then be tested by fluorescence of the site where the fragment hybridizes, by scanning a particular light frequency across the site identifying whether the fragment is present in the sample.

Biological arrays can be used for gene sequencing. In general, gene sequencing involves determining the size of a nucleotide or nucleic acid, such as a DNA or RNA fragment, in the length of the genetic material. The longer sequences of base pairs are analyzed and the resulting sequence information can be used in a variety of bioinformatics methods that locally fit fragments together to easily determine the vast length sequences of genetic material derived from fragments. have. Automated, computer-based tests of characteristic fragments have been developed and used in the evaluation of genome mapping, identification of genes and their functions, specific conditions and disease states, and the like. Beyond these applications, biological arrays can be used for various molecules, molecular families, gene expression levels, detection and evaluation of single nucleotide polymorphisms, and genotyping.

An example of an imprinting device includes a silicon master having a plurality of defined nanofeatures. Exemplary anti-stick layers coat the silicone master, wherein the anti-stick layer comprises molecules having cyclosiloxanes with at least one silane functionality.

Examples of methods include depositing a formulation on a silicon master comprising a plurality of defined nanofeatures, wherein the formulation comprises a solvent and a molecule having a cyclosiloxane having at least one silane functional group; And forming a master mold by forming an anti-stick layer on the silicone master by curing the formulation, wherein the anti-stick layer comprises molecules. The method includes depositing a silicon-based work stamp material on an anti-stick layer of a master mold; Curing the silicone based work stamp material to form a work stamp comprising a plurality of nanofeatures negative replicas; And releasing the work stamp from the master mold.

The features and advantages of the present disclosure examples will become apparent with reference to the following detailed description and drawings, wherein like reference numerals correspond similarly, although they are not identical components. For brevity, reference numerals or features having the functions described above may or may not be described with respect to other drawings in which they appear.
1 shows a top view of an exemplary silicon master wafer;
2A-2E are semi-schematic illustrations of an example of a method of forming a work stamp together;
3A-3E show schematically an example of a method of forming a surface using an example of a work stamp together;
4 shows an additional enlarged view of a scanning electron microscopy (SEM) image of the cutaway on the left side, an imprinted substrate surface (shown in the middle) of a partially cross-sectional area, and a single well with a plurality of surface functional groups on the right side. Illustrated;
FIG. 5 shows, in one embodiment, a first produced from a master coated with a comparative anti-stick layer as compared to the first and fifth work stamps (two sets of bars on the right) produced from a master coated with an exemplary anti-stick layer. And a bar graph showing the surface roughness between the first imprint and the last imprint, using a fifth work stamp (two sets of bars on the left side);
6 shows, in one embodiment, a bar graph showing surface roughness progression as a function of job stamp generation and imprint number;
FIG. 7A shows a 30 μm atomic-force microscopy (AFM) image of an exemplary imprinted substrate surface plan view formed from a 25th imprint produced from a fifth generation work stamp produced from a master coated with an exemplary anti-stick layer. Illustrated;
FIG. 7B shows a 5 μm atomic force microscope (AFM) image of FIG. 7A;
FIG. 8A shows a top down SEM image of an example imprinted substrate surface formed by a work stamp produced from a master coated with an example anti-stick layer exhibiting a desirable level of pattern accuracy / round wells and no detectable bonds;
FIG. 8B shows a cross-sectional SEM image of the imprinted substrate of FIG. 8A showing well defined well cross-sectional area / sharp well edges. FIG.
FIG. 9A shows a top down SEM image of an imprinted substrate surface formed by a work stamp produced from a master coated with a comparative anti-stick layer, exhibiting a desirable level of pattern accuracy; And
9B shows a cross-sectional SEM image of the imprinted substrate of FIG. 9A showing a less defined well cross section and rounded well edges.

Introduction

In an aspect, the imprinting device comprises a silicon master comprising a plurality of defined nanofeatures. The anti-stick layer coats the silicon master, wherein the anti-stick layer comprises molecules having cyclosiloxanes having at least one silane functional group.

In some examples of this aspect, a cyclosiloxane having at least one silane-functional group is a cycloalkyl substituted with at least one C _{1- 12} alkyl group which is substituted with a, and an alkoxysilane substituted by C _{1- 6} alkyl group the ring at least one Beach Siloxanes (eg, cyclotetrasiloxane, cyclopentasiloxane, or cyclohexasiloxane). In another example of this aspect, cyclosiloxanes having at least one silane functional group are cyclosiloxanes (eg cyclo) substituted with four unsubstituted C _1-6 alkyl groups and four C _1-12 alkyl groups, each substituted with an alkoxysilane group. Tetrasiloxane, cyclopentasiloxane or cyclohexasiloxane). In some instances, C _{1- 6} alkyl group is a methyl group. In another example, C _{1- 12} alkyl groups are each substituted by a tri-alkoxy silane, and an ethyl or propyl group which is substituted in some instances, and is in some instances, the substituted group. In some instances, the alkoxysilane is a monoalkoxysilane. In some instances, the alkoxysilane is a trialkoxysilane. In some instances, the trialkoxysilane group is trimethoxysilane or triethoxysilane. In some instances, the trialkoxysilane group is triethoxysilane. In some instances, the anti-stick layer comprises a mixture of cyclosiloxanes.

In one example of this aspect, the molecule is as follows:

.

.

In one example of this aspect, the anti-stick layer comprises a mixture of molecules in their pure form and oligomers of the molecules. In another example of this aspect, the anti-stick layer comprises a mixture of molecules and at least one other cyclosiloxane.

In one example of this aspect, the cyclosiloxane is selected from the group consisting of cyclotetrasiloxane and cyclohexasiloxane.

In one example of this aspect, the silane functional group is an alkyl alkoxysilane.

In one example of this aspect, the alkyl alkoxysilane is ethyl triethoxysilane.

In one example of this aspect, the imprinting apparatus further includes a silicon based work stamp in contact with the anti-stick layer on the silicon master.

In one example of this aspect, the silicone-based work stamp includes a polymerized silicone acrylate monomer.

In one example of this aspect, the imprinting apparatus further comprises a back plate in contact with the work stamp.

In one example of this aspect, the molecule excludes fluorine. In some instances, the anti-stick layer excludes fluorine or excludes fluorine-containing compounds.

It should be understood that any of the features of this aspect of the imprinting device may be combined together in any desired manner and / or configuration.

In an aspect, forming a master template by depositing a formulation on a silicon master comprising a plurality of defined nanofeatures. The formulation comprises a solvent and a molecule having a cyclosiloxane with at least one silane functional group. In some aspects, the method includes cleaning the surface of the silicon master, eg, by plasma material or chemical cleaning, prior to depositing the formulation. The method further comprises forming an anti-stick layer on the silicone master by curing the formulation, the anti-stick layer comprising molecules. The method further includes depositing a silicon based work stamp material on the anti-stick layer of the master mold, and curing the silicon based work stamp material to form a work stamp comprising a plurality of nanofeature negative copies. The method also includes releasing the work stamp from the master mold. In some aspects, the silicon master comprises silicon or silicon-SiO ₂ layered material.

In one example of this aspect of the method, the solvent has a boiling point of less than about 70 ° C. In some examples, the molecule is present in the formulation in an amount of at least about 5% by weight.

In one example of this aspect of the method, the solvent is tetrahydrofuran or toluene and / or the molecule is as follows:

.

.

In one example of this aspect of the method, depositing the formulation and depositing the silicon based work stamp material each involve spin coating.

In one example of this aspect of the method, the silicone-based work stamp material comprises a silicone acrylate monomer.

In one example of this aspect of the method, the molecule is present in the formulation in an amount ranging from about 5% to about 10% by weight.

In some aspects, the step of releasing serves to release the work stamp from the master mold and from the cured anti-stick layer. In one example of this aspect of the method, the released work stamp is at least substantially free of molecules.

In some aspects, the released master template may be further repeated in a work stamp (eg, greater than 1, greater than 5, greater than 10, greater than 25, greater than 50, 1 to 10, 1 to 25, 1 to 50, 25 to 50, etc. ) Is reused to manufacture. In some aspects, the released master mold includes an anti-stick layer and is reused without reapplying the anti-stick layer. In some aspects, reuse of the released master mold comprises depositing a second silicon-based work stamp material on the anti-stick layer of the released master mold; Curing the second silicon-based work stamp material to form a second work stamp comprising a plurality of nanofeatures of nano replicas; And releasing the second work stamp from the released master mold. In some aspects, the reuse process is repeated multiple times (eg, 2, 5, 10, 25 or 50 times). In some aspects, reuse of the released master template includes reapplication of an anti-stick layer, thus depositing a formulation comprising a solvent and a molecule having a cyclosiloxane having at least one silane functional group on the released master template; Forming an anti-stick layer on the master mold released by curing the formulation, wherein the anti-stick layer comprises molecules; Depositing a silicon based work stamp material on the anti-stick layer of the released master mold; Curing the silicon-based work stamp material to form a second work stamp comprising a plurality of nanofeatures negative copies; And releasing the second work stamp from the released master mold. In some aspects, the reuse method includes cleaning the released master template, eg, by plasma material or chemical cleaning, prior to depositing the formulation. This process can be repeated multiple times (eg, 2, 5, 10, 25 or 50 times) using the same master template.

It should be understood that any feature of this aspect of the method may be combined together in any desired manner. In addition, any combination of features of this aspect of the method and / or aspects of the imprinting apparatus may be used together, and / or any feature from one or both of these aspects may be used in any of the examples disclosed herein. It should be understood that it can be combined with.

In an aspect, a method using a work stamp (formed by aspect (s) of the method discussed above) includes imprinting the work stamp on an imprint lithography resin on a support; And curing the resin to form a sequencing surface having a plurality of replicas of the nanofeatures defined (eg, negative replicas of the work stamp features, thereby matching the original master template features).

In one example of this aspect of the method of use, the sequencing surface is at least substantially free of molecules.

In one example of this aspect of the method of use, the method further comprises conjugating the amplification primers on the intermediate structures present in the plurality of nanofeature copies. In another aspect of the method of use, the method further comprises conjugating the intermediate structure to the patterned sequencing surface in the defined plurality of nanofeature copies. In another aspect, the method further comprises conjugating the amplification primers to the intermediate structures in the replica of the plurality of nanofeatures on the sequencing surface.

In one example of this aspect of the method of use, the intermediate structure is a polymeric coating comprising repeating units of formula (I):

During the formula:

R ¹ is H or optionally substituted alkyl;

R ^A is azido, optionally substituted amino, optionally substituted alkenyl, optionally substituted hydrazone, optionally substituted hydrazine, carboxyl, hydroxy, optionally substituted tetrazole, optionally substituted tetra Selected from the group consisting of gin, nitrile oxide, nitrone and thiol;

R ⁵ is selected from the group consisting of H and optionally substituted alkyl;

Each — (CH ₂ ) _p — may be optionally substituted;

p is an integer ranging from 1 to 50;

n is an integer ranging from 1 to 50,000; And

m is an integer ranging from 1 to 100,000.

One skilled in the art is representative of the arrangement of the "n" and "m" features repeated in Formula (I), wherein the monomer subunits are in any order in the polymer structure (eg, random, block, patterned, or a combination thereof). It will be appreciated that it can exist.

It should be understood that any feature of this aspect of the method of use may be combined together in any desired manner. In addition, any combination of the features of this aspect of the method of use and / or the aspect of the method and / or of the aspect of the imprinting device may be used together, and / or any feature from one or both of these aspects It should be understood that it may be combined with any of the examples disclosed herein.

Detailed description of the invention

Incorporating patterning techniques (localized and independent clusters) into gene sequencing can improve sequencing quality. However, creating a patterned flow cell by traditional lithography techniques (pattern definition through the use of photons or electrons) involves a number of processing steps per first class clean room and wafer.

Examples of the disclosure may advantageously be measurable from die-level processes to wafer-level processes.

Nanoimprint lithography (NIL) may be a relatively high speed bulk patterning technique that provides high precision and low cost. However, we note that in some instances standard NILs are not generally suitable for use in flow cell preparation (eg, due to sequencing complexity from characteristic sizes, etc.) and may effectively support gene sequencing surface chemistry. Found none.

Fabrication of imprinted wafers using NIL generally involves i) fabrication of a working stamp (WS) (negative copy of the master); And replicating the master pattern (model) to the resin substrate using an initially prepared WS (imprinting process).

However, it has been found that the fabrication of WS cannot be automated using pre-existing equipment and materials. Once spin coated on a master coated with an anti-stick layer (ASL), the WS formulation was de-wetting very quickly from the surface to repeatedly provide a suitable stamp. The WS manufacturing stage has a low success rate, thus making the overall NIL process unusable for automated production. Although not bound by any particular theory, the inventors believe that surface energy mismatches between the coated master and the WS material may be due to this phenomenon.

Examples of the present disclosure describe a class of new materials to be used as efficient ASL. The exemplary ASL-coated master obtained provides stable WS formulation wetting, thus resulting in a systematic successful WS fabrication process. In addition, the process can be automated at high success rates.

It is to be understood that the terminology used herein, unless otherwise specified, will take their ordinary meaning in the appropriate description. Some terms used herein and their meanings are set forth below.

The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.

It is to be understood that the various forms of these terms are included and that the terms they contain are synonymous with one another and equally broad.

As used herein, the term “depositing” refers to any suitable application technique that can be manual or automated. In general, deposition may be performed using deposition techniques, coating techniques, bonding techniques, and the like. Some specific examples include chemical vapor deposition (CVD), spray coating, spin coating, dunk or dip coating, puddle dispensing, and the like.

The term “depression” as used herein refers to a distinct concave feature in a patterned wafer having a surface opening that is completely surrounded by interstitial region (s) of the patterned wafer surface. The recesses may have any of a variety of shapes at their openings in the surface, including, for example, circular, elliptical, square, polygonal, star (with multiple vertices), and the like. The cross-sectional areas of the recesses taken perpendicular to the surface may be curved, square, polygonal, hyperbolic, conical, angular, or the like. By way of example, the concave surface may be a well or a flow passage.

As used herein, the term "hard baking" or "hard bake" refers to incubating or dehydrating the polymer formulation to drive off the solvent (s), wherein the duration of the process is usually about Lasting from about 5 seconds to about 10 minutes at a temperature in the range from 100 ° C to about 300 ° C. Non-limiting examples of devices that can be used for hard baking include hot plates.

As used herein, the term "feature" or "nanocharacteristic" is intended to mean a separate physical element or separate physical attribute of a substrate. Features / nanocharacteristics include the distinguishable physical or structural attributes of the substrate. Thus, the feature is that part of the substrate that provides physical separability. The feature separates, for example, the biopolymer deposited in the first feature from the biopolymer deposited in the second feature.

As used herein, the term “soft baking” or “soft bake” refers to a process of incubating or dehydrating a polymer or hydrogel formulation to drive off the solvent (s), the duration of the process usually being about 60 ° C. Lasting from about 5 seconds to about 10 minutes at a temperature in the range from about 130 ° C. Non-limiting examples of devices that can be used for soft baking include hot plates.

Referring now to FIGS. 1 and 2A-2E, a plurality of silicon masters, one of which is designated 10, is disposed on wafer 11 (eg, a silicon wafer). After the processing described below with respect to FIGS. 2A-2E, it should be understood that a plurality of work stamps 16 ′ may be formed from a single wafer 11. It is to be understood that other materials may be used as the master 10, such as a metal, for example nickel. In the example, master 10 is a silicon oxide master. Master 10 includes a plurality of defined nanofeatures 12 (FIG. 2A). It is to be understood that the nanofeatures may have any suitable shape, size and / or conformation. In an example, the nanofeature 12 is in the shape of at least substantially cylindrical recesses / wells formed from a single work stamp 16 ′ (see, eg, FIG. 4, left).

According to an example of the method disclosed herein, the master 10 can be cleaned and dried. Subsequently, an anti-stick layer (ASL) formulation comprising a solvent and a molecule having a cyclosiloxane having at least one silane functional group is deposited on the master 10 and on the plurality of nanofeatures 12.

It should be understood that any suitable solvent may be used. By way of example, the solvent is an organic solvent. By way of example, the solvent has a boiling point of about 110 ° C. or less; And in further examples, the solvent has a boiling point of less than about 70 ° C. By way of example, the solvent is selected from the group consisting of tetrahydrofuran (THF) (boiling point is 66 ° C.) and toluene (boiling point is 110 ° C.). In another embodiment, the solvent has a boiling point of about 60 ° C to about 150 ° C.

By way of example, the molecules are present in the ASL formulation in an amount of at least about 5% by weight. As another example, the molecules are present in the ASL formulation in an amount ranging from about 5% to about 10% by weight. In another example, the molecule is present in the ASL formulation in an amount ranging from about 10% to about 20% by weight. As used herein, the term “molecule” present in an ASL formulation includes: i) a molecule in its pure form; And / or ii) a mixture of molecules in their pure form and oligomer (s) of the molecule.

It should be understood that any suitable deposition method may be used. As an example, the ASL layer formulation is spin coated onto the master 10. As another example, the ASL formulation can be deposited via a chemical vapor deposition (CVD) process. In a further example, the ASL formulation can be deposited via any spray coating, dunk or dip coating or puddle dispensing.

The method may further comprise forming an anti-stick layer 14 on the master 10 by curing the ASL formulation, the anti-stick layer comprising molecules (FIG. 2B). As an example, ASL formulations are thermally cured. In some examples, thermal curing may be performed at a temperature in the range of about 60 ° C to about 220 ° C. While an exemplary range has been provided, it should be understood that the thermal cure temperature may be higher or lower depending on the system and / or solvent in use. By way of example, the temperature range may be about 40 ° C to about 60 ° C, or about 220 ° C to about 240 ° C.

The master 10 having the anti-stick layer 14 is a master mold generally indicated at 10 'in FIG. 2B. The master mold 10 'can then be washed with a solvent. The washing step serves to remove excess and / or unreacted material.

Examples of the anti-stick layer 14 include molecules with cyclosiloxanes having at least one silane functional group. By way of example, the molecules are as follows:

.

.

By way of example, an ASL formulation (formed from the anti-stick layer 14 after deposition and curing) comprises a mixture of molecules in their pure form and oligomers of the molecules (eg dimers and trimers), ie ASL formulation / departure The ASL material may not only be composed of small molecules but also may be a mixture of small molecules and molecular oligomers. After the ASL curing step on the master, the ratio of pure (small molecule) to oligomer can be advantageously influenced by the oligomeric species. Polymerization of ASL molecules can be triggered by heat. Without being bound by any theory, a mixture of pure and oligomeric molecules (macromolecules) may well cover a large portion of the surface, while smaller molecules may be left uncovered by oligomeric molecules ( It is believed that it can be reacted. However, it should be understood that in further examples, ASL formulations may contain pure molecules without oligomeric molecules.

By way of example, the ASL formulation includes an amount of oligomer in the range of about 0% to about 35% by weight, and includes an amount of pure compound in the range of about 100% to about 65% by weight. As another example, the ASL formulation includes an amount of oligomer in the range of about 20% to about 30% by weight, and includes an amount of pure compound in the range of about 80% to about 70% by weight. In another example, the ASL formulation includes an oligomer amount in the range of about 20% to about 23% by weight and comprises an amount of pure compound in the range of about 80% to about 77% by weight. In a further example, the ASL formulation is 100% pure compound. Regardless of the ASL formulation composition (ie, pure to oligomer weight percent), the performance of the ASL material is believed to be at least substantially unchanged.

In the example using a mixture of pure compound and oligomeric compound (ie not 100% pure compound), the molecules are present in the ASL formulation in an amount of about 5% by weight. In an example using 100% pure compounds, the molecules are present in the ASL formulation in an amount of about 10% by weight.

In one non-limiting example, the inventors have found that molecules present in the ASL formulation in an amount of about 10% by weight based on about 5% by weight pure material relative to the pure / oligomeric mixture are generally produced with a consistent working stamp 16 '. It was found that it was the lowest concentration that was successful in imprinting (preferred level of pattern accuracy and / or low / controlled roughness (discussed further below)). In this example, the results indicate that acceptable ASL uniformity is achieved for the 5/10% by weight formulation, thereby resulting in a smoother imprinting surface. In comparison, lower concentrations can result in "uneven" coatings and can result in increased roughness. In some examples, weight percentages greater than 5% by weight for pure / oligomeric mixtures and weight percentages greater than 10% by weight for pure materials are used. However, as mentioned above, lower concentrations may produce undesirable results.

The number average and weight average molecular weight of a molecule having a cyclosiloxane with at least one silane functional group may depend, in part, on the percentage of pure compounds and / or oligomers present. By way of example, the number average molecular weight is in the range of about 1280 to about 1600 and / or the weight average molecular weight is in the range of about 1800 to about 3700. Molecular weight determinations can be made by gel permeation chromatography (GPC) and / or NMR.

It should be understood that any suitable cyclosiloxane can be used. By way of example, the cyclosiloxane is selected from the group consisting of cyclotetrasiloxane and cyclohexasiloxane. A wide variety of cyclosiloxanes of varying ring sizes, for example, assume that suitable ASL formulations of 4 to 24 repeating units (-[H ₂ SiO] _n- ), most commonly 6 to 8 membered rings, are suitable. Should be further understood. Ring size is a repeat of the Si-O motif and should be even. As the ring size grows larger, mixtures of rings with different sizes may predominate, but this is also assumed to be a suitable example of an ASL formulation.

By way of example, the silane functional group (s) of the cyclosiloxane molecule is an alkyl alkoxysilane. In a further example, the spacer between the cyclosiloxane and the alkoxy or ethoxy silane group could include various chemical groups, such as amino groups, double or triple bonds, ester groups, polyethylene glycol units, and the like. In a further example, the alkyl alkoxysilane is ethyl triethoxysilane.

It should be understood that the length of the spacer does not affect the affinity for the alkoxysilane to the bond to the master 10. The most common spacer lengths are C2 to C12 chains. In some instances, the alkoxysilane group is tri- or mono-methoxysilane or tri- or mono-ethoxysilane, or in other examples, tri-, di- or mono-chlorosilanes may be used. In some instances, the alkoxysilane group is a dialkyl-alkoxysilane, wherein the alkyl group is a C 1-6 alkyl group, such as a methyl or ethyl group. However, the terminal group is not methyl silane or ethyl silane because it needs to contain a chemical group that can react with the surface of the master 10.

In further examples, the ASL molecule excludes fluorine. It has been found that ASL molecules disclosed herein, except for fluorine, have surface energy suitable for working stamp materials other than fluorinated compounds (eg, silicon-based material 16) and result in their efficient wetting.

An example of the method further includes depositing a silicon based material 16 (to form a work stamp) on the anti-stick layer 14 of the master mold 10 '(FIG. 2C). "Silicone-based" material as used herein means that the material consists of at least about 50 mol% silicon-containing molecules (repeating monomer units). As an example, the silicon-based WS material 16 consists of about 100 mol% silicon-containing molecules (repeating monomer units). In further examples, WS material 16 may be a silicon-containing polymer (ie, a polymer having less than about 50 mol% silicon containing molecules). In another example, the WS material includes silicone acrylates. In another example, the WS material also includes at least one photoinitiator.

It should be understood that any suitable deposition method may be used. Examples of suitable deposition techniques include spray coating, spin coating, dunk or dip coating, puddle dispensing, and the like. By way of example, the silicon based material 16 is spin coated onto the master mold 10 '.

The method comprises curing a silicon-based material 16 to form a work stamp 16 ′ comprising a negative copy of a plurality of nanofeatures 12 in contact with the anti-stick layer 14 on the silicon master 10 ( 2D). By way of example, the work stamp material 16 is cured through ultraviolet (UV) radiation. As another example, the WS material 16 is thermally cured. In some examples, thermal curing can be performed at a temperature in the range of about 60 ° C to about 300 ° C. As used herein, the term "contact" can include physical contact between components.

The method may further comprise attaching a backplate to the work stamp 16 '. By way of example, a polymer film comprising the adhesive material 20 may be applied (eg, by roll coating) to the work stamp material 16 such that the adhesive is in contact with the work stamp material 16. . Then, when exposed to UV radiation, the work stamp 16 'will be bonded to the backplate 18 by curing both the work stamp material 16 and the adhesive material 20. It should be understood that the backplate 18 may be formed from any suitable polymeric material. By way of example, the backplate 18 is a polyethylene terephthalate (PET) film. Other examples of backplate 18 include poly (vinyl chloride) (PVC) and propylene oxide (PO). In some aspects, the backplate material is flexible. It should further be appreciated that the adhesive material may be any suitable UV curable material.

The method further includes releasing the work stamp 16 'from the master mold 10'. It should be understood that the release may be by any suitable means. By way of example, ejecting is by unrolling / filling the hardened work stamp 16 'from the master mold 10'.

It should be understood that the work stamp (WS) material 16 may be any material that meets the following. WS material 16 must be stable and can be coated / formed on master mold 10 '. Stable, this means that once fabricated, the WS 16 'must remain unchanged (no decomposition) until its final use (life cycle). WS 16 ′ should support room temperature storage for at least one month after fabrication and during repeated UV exposure (eg, an imprinting process). Repeating UV exposure should not change the toughness / flexibility of WS 16 'by increasing the crosslink density. The resulting WS 16 'must be ductile / flexible, but must also exhibit suitable mechanical properties. For example, the WS 16 'must be soft enough to support rolling on the resin (not full rolling around the cylinder) and delamination after resin curing during the imprinting process; It should not be extensible so that it can maintain good dimensional and pattern accuracy between imprints. For example, WS 16 'must be resistant to deformation and to cracks / ruptures. As an example, the WS 16 'should not show any deformation in producing consistent characteristic dimensions. In addition, the WS face 22 should have a desirable level of antistick surface properties (eg, for the resin to be imprinted); WS 16 'must be chemically stable (as described above for stability); And the WS 16 'must be resistant to a large degree of expansion. With regard to surface properties, the cured WS 16 'should have a suitable surface tension to provide for successful removal of the WS 16' from the imprinting surface. Resistance to expansion is specific to the working stamp material 16 as well as the solvent used for the resin formulation. WS 16 ′ should not be expanded in either the WS manufacturing stage or the imprinting stage. Expansion may result in feature size or dimensional changes.

As an example, the silicone based work stamp 16 ′ is made from polymerized silicone acrylate monomers (ie, 100 mol% silicon containing molecules consisting of a single monomer, which is a homopolymer). This can prevent heterogeneity of the final polymer (eg, the copolymer can lead to phase separation, gradient of polymer chains).

In a further example, the released work stamp 16 ′ is at least substantially free (ie, absent or substantially free) of ASL molecules. Without being bound by any theory, delivery of ASL molecules should not occur during the WS 16 'fabrication process because any excess unreacted ASL molecules must be washed prior to fabrication of the first WS 16'. (Ie no ASL molecule). If any molecule is delivered, it is at most parts per million (ppm), so WS (16 ') is believed to be substantially free of ASL molecules.

We have found that the choice of ASL and WS materials is important for effective WS fabrication. There must be a suitable surface energy match between the ASL-coated master (master template 10 ') and the work stamp material 16. This, in turn, should provide both suitable surface wetting and effective stamp detachment. In addition, stamp robustness / integrity through imprint should be obtained by the selection of a WS material that meets the details set out above.

The ASL materials 14 disclosed herein utilize a nano-imprint lithography (NIL) process to systematically efficient wetting from the master mold 10 ', flat WS 16' detachment, and high quality imprint (preferably at a pattern accuracy). And low surface roughness) allows the use of silicon-based WS materials in automated processes. It should be understood that proper wetting and stamp release do not always result in the desired imprint quality. In this way, an example of ASL material disclosed herein (if successful through the fabrication of WS 16 ') is tested and verified by the imprint test plan.

According to examples of the present disclosure, both polymeric compounds and small molecules can be considered for ASL material 14.

It should be understood that the ASL material 14 can be any material that meets the following details. The ASL material 14 must be a thermally stable compound (to withstand firing). The ASL material 14 should also be a UV stable compound (eg, to withstand repeated WS 16 ′ fabrication processes). The ASL material 14 coated on the silicon master must withstand at least about 1 month after being coated at room temperature (eg, temperature in the instrument) and undergoes repeated UV exposure (ie, WS 16 'fabrication process). Must support ASL materials should exhibit a positive contact angle of greater than about 80 ° (with water). By way of example, the contact angle ranges from about 80 ° to about 110 ° (with water). Further, as an example, there is a surface energy match between the ASL-coated master mold 10 ′ and the work stamp material 16. The surface energy used herein may be considered to be matched when the positive contact angle of the ASL material 14 (using water) is within about +/− 10 degrees of the positive contact angle of the WS material 16. Suitable surface energy match can be achieved, for example, when the ASL-coated master mold 10 'has an average contact angle of about 90 ° (with water), the work stamp material 16 is (water Have an average contact angle in the range of about 95 ° to about 100 °. Contact angles disclosed herein are measurements / values collected from a persistent surface, not from patterned areas.

Referring now to FIGS. 3A-3E, an example of a method of using an example of a work stamp 16 ′ is shown.

The substrate / support 24 is provided as shown in FIG. 3A. By way of example, the substrate 24 is glass. However, it should be understood that any suitable substrate may be used.

For example, some suitable substrates 24 include silica-based substrates such as glass, fused silica, and other silica-containing materials. In some examples, the silicon based substrate may also be selected from silicon, modified silicon, silicon dioxide, silicon nitride and silicon hydride. In another example, the substrate 24 material may be a plastic / polymer material such as acrylic acid, polyethylene, polystyrene, and copolymers of styrene and other materials, poly (vinyl chloride), polypropylene, polybutylene, nylon, poly Esters, polycarbonates and poly (methyl methacrylates), polyurethanes, polytetrafluoroethylene (PTFE) (e.g. TEFLON® from Chemours), cyclic olefins / cyclo-olefins It should be understood that it may be selected from polymers (COPs) or copolymers (COCs) (eg, ZEONOR® from Zeon, polyimide, etc.). By way of example, the polymer base material is selected from poly (methyl methacrylate), polystyrene and cyclic olefin polymer bases. In a further example, the substrate 24 has at least one surface that is glass, modified glass or functionalized glass. Other suitable substrate materials also include ceramics, carbon, inorganic glass, and optical fibers. While some examples have been provided, it should be understood that any other suitable substrate / support may be used.

In some other examples, the substrate can be a metal. By way of example, the metal is gold. In some examples, substrate 24 has at least one surface that is a metal oxide. In one example, the surface is tantalum oxide or titanium oxide. It should be understood that acrylamide, enon (α, β-unsaturated carbonyl), or acrylates may also be used as the base material. Other substrate materials may include gallium arsenide (GaAs), indium tin oxide (ITO), indium phosphide, aluminum, ceramics, polyimide, quartz, resins, aryl azides, polymers and copolymers.

In some examples, substrate 24 and / or substrate surface S may be quartz. In some other examples, substrate 24 and / or substrate surface S may be a semiconductor, such as gallium arsenide (GaAs) or indium tin oxide (ITO).

Exemplary substrates may include a single material or a plurality of different materials. In further examples, the substrate may be a composite or laminate. Also in further examples, the substrate may be flat and round.

An exemplary method of using the WS 16 ′ may further include depositing an adhesion / prime layer 26 on the surface S of the substrate / support 24 as shown in FIG. 3B. Suitable compounds for the adhesion / prime layer 26 should have two functional groups: one which reacts with the substrate surface S and one which reacts with the imprint lithography resin 28. Groups reacting with the surface (S) are, for example, alkoxysilane groups such as tri or mono methoxysilane or tri or mono ethoxysilane; Or tri, di or monochlorosilane; Or a dialkyl-alkoxysilane group. The group reacting with the resin 28 may be, for example, an epoxy group, an amino group, a hydroxyl group or a carboxylic acid group. The skeleton of the molecule connecting the two reactors can have any properties.

An exemplary method using WS 16 ′ is to deposit an imprint lithography resin (eg, photocurable (when using UV curing) nano-imprint lithography (NIL) polymer resin) 28 on support 24. Step (FIG. 3C). After soft firing of resin 28 to remove excess solvent, WS 16 ′ imprints on resin 28 such that resin layer 28 is squeezed or perforated by teeth of WS 16 ′. It is pressed against the resin 28 layer to produce (FIG. 3D). The method still further includes curing the resin 28 (eg, by exposing the resin 28 to ultraviolet (UV) radiation). As another example, thermal curing may be used. For the thermally induced curing process, the temperature can be as high as 550 ° C. and the force applied to the resin 28 (from WS 16 ′) can be as high as 360 kN. For the soft materials disclosed herein, lower temperatures and pressures can be used.

After curing, the work stamp 16 ′ is released, thereby having a replica of the plurality of master 10 nanofeatures 12 (FIG. 3E), and patterning sequencing surfaces defining the wells / concaves 31. 30) (the surface comprising chemical functional groups 32, or in which subsequent chemical functional groups 32 are added, see FIG. 4). The term "sequencing surface" as used herein refers to a surface capable of supporting gene sequencing surface chemistry (eg, intermediate structure 34 and proliferation primer 36).

Substrate 24 with patterned sequencing surface 30 may be heat cured / hard calcined to complete UV curing and locked in imprint topography. In some examples, thermal curing / hard firing may be performed at a temperature in the range of about 60 ° C to about 300 ° C.

In some examples, functional groups X, Y of chemical functional group 32 (FIG. 4) are in the well surface of the flow cell and / or in the region in contact with the flow cell passage lumen. Functional groups (X, Y) may be available for further functionalization to capture single stranded DNA (ssDNA) for DNA sequencing procedures, if desired. This functionalization process may or may not include the selective capture of a polymer support (eg, PAZAM, discussed further below) on the flow cell well surface 30. The functional groups (X, Y) may also or alternatively serve as anchor points for further modification.

By way of example, sequencing surface 30 may be at least substantially free (ie, absent or substantially free) of an ASL molecule (eg, as mentioned above with respect to work stamp 16 ′), If none is on sequencing surface 30 (no ASL molecules), or if any molecule is delivered, it is believed to be at most parts per million (ppm) level. In addition, sequencing surface 30 with gene sequencing surface chemistry is also at least substantially free of ASL molecules.

In an example of a method using sequencing surface 30, intermediate structure 34 is deposited in well 31. Well 31 may have a microwell (at least one dimension on a micron scale, eg, about 1 μm to about 1000 μm) or a nanowell (at least one dimension on a nanoscale, eg, about 1 Nm to about 1000 nm). Each well 31 may be characterized by its volume, well opening area, depth and / or diameter.

Each well 31 may have any volume capable of confining the liquid. The minimum or maximum volume can be selected to accommodate the expected throughput (eg, multiplicity), resolution, assay composition or analyte reactivity, for example, for downstream use of sequencing surface 30. For example, the volume may be at least about 1 × 10 ⁻³ μm ³ , about 1 × 10 ⁻² μm ³ , about 0.1 μm ³ , about 1 μm ³ , about 10 μm ³ , about 100 μm ^{3 or} more. Alternatively or additionally, the volume may be up to about 1 × 10 ⁴ μm ³ , about 1 × 10 ³ μm ³ , about 100 μm ³ , about 10 μm ³ , about 1 μm ³ , about 0.1 μm ³ or less. It should be understood that the intermediate structure 34 may fill all or part of the volume of the well 31. The volume of the intermediate structure 34 in the individual wells 31 may be above, below or between the specified values.

The area occupied by each well opening on the surface can be selected based on criteria similar to those set forth above for each volume. For example, the area for each well opening on the surface may be at least about 1 × 10 ⁻³ μm ² , about 1 × 10 ⁻² μm ² , about 0.1 μm ² , about 1 μm ² , about 10 μm ² , about 100 May be at least ² μm. Alternatively or additionally, the area may be up to about 1 × 10 ³ μm ² , about 100 μm ² , about 10 μm ² , about 1 μm ² , about 0.1 μm ² , about 1 × 10 ⁻² μm ² or less.

The depth of each well 16 ′ may be at least about 0.1 μm, about 1 μm, about 10 μm, about 100 μm or more. Alternatively or additionally, the depth may be up to about 1 × 10 ³ μm, about 100 μm, about 10 μm, about 1 μm, about 0.1 μm or less.

In some examples, the diameter of each well 16 ′ may be at least about 50 nm, about 0.1 μm, about 0.5 μm, about 1 μm, about 10 μm, about 100 μm or more. Alternatively or additionally, the diameter may be up to about 1 × 10 ³ μm, about 100 μm, about 10 μm, about 1 μm, about 0.5 μm, about 0.1 μm, about 50 nm or less.

In the sequencing plane 30, the intermediate structure 34 is located in each separate well 31. The positioning of the intermediate structure 34 in each well 31 first coats the patterned surface 30 with the intermediate structure 34, and then at least the interstitial region on the surface 30 between the wells 31. From (33), for example, by removing the intermediate structure 34 through chemical or mechanical polishing. These processes retain at least a portion of the intermediate structure 34 in the well 31, but remove at least substantially all of the intermediate structure 34 from the interstitial region 33 on the surface 30 between the wells 31. Or disable it. In this way, these processes produce gel pads 34 that are used for sequencing that can be stable over sequencing runs in a very large number of cycles (FIG. 4).

A particularly useful intermediate structure 34 will identify the shape of the site in which it is present. Some useful intermediate structures 34 correspond to (a) the shape of the site where it is present (eg, well 31 or other recess features) and (b) at least substantially exceed the volume of the site where it is present. May have a volume.

In an example, the intermediate structure is a polymer / gel coating. Examples of suitable gel materials for the intermediate structure 34 include polymers having repeat units of formula (I):

During the formula:

R ¹ is H or optionally substituted alkyl;

R ^A is azido, optionally substituted amino, optionally substituted alkenyl, optionally substituted hydrazone, optionally substituted hydrazine, carboxyl, hydroxy, optionally substituted tetrazole, optionally substituted tetra Selected from the group consisting of gin, nitrile oxide, nitrone and thiol;

R ⁵ is selected from the group consisting of H and optionally substituted alkyl;

Each — (CH ₂ ) _p — may be optionally substituted;

p is an integer ranging from 1 to 50;

n is an integer ranging from 1 to 50,000; And

m is an integer ranging from 1 to 100,000.

Suitable polymers for formula (I) are described, for example, in US Patent Publication No. 2014/0079923 A1 or 2015/0005447 A1, each of which is incorporated herein by reference in its entirety. In the structure of formula (I), those skilled in the art will understand that the "n" and "m" subunits are repeating subunits present in random order throughout the polymer.

Specific examples of polymer coatings, such as formula (I), are poly (N- (5-azidoacetamylpentyl) acrylamide-co-acrylamides (PAZAM), and include, for example, the structures shown below. US Patent Publication No. 2014/0079923 A1 or 2015/0005447 A1:

n is an integer ranging from 1 to 20,000 and m is an integer ranging from 1 to 100,000. According to formula (I), one skilled in the art will recognize that the "n" and "m" subunits are repeat units that exist in random order throughout the polymer structure.

The molecular weight of the polymer of formula (I) or PAZAM polymer may range from about 10 kDa to 1500 kD, or in specific examples, may be about 312 kDa.

In some instances, Formula (I) or PAZAM polymer is a linear polymer. In some other examples, Formula (I) or PAZAM polymer is a lightly crosslinked polymer. In another example, Formula (I) or PAZAM polymers include branching.

Other examples of suitable gel materials for the intermediate structure 34 include those having a colloidal structure, such as agarose; Or polymeric mesh structures such as gelatin; Or cross-linked polymer structures such as polyacrylamide polymers and copolymers, silane acrylamide (SFA, see, eg, US Patent Publication No. 2011/0059865, incorporated herein by reference), or azizated of SFA Include form. Examples of suitable polyacrylamide polymers are, for example, from acrylamide and acrylic acid containing acrylic acid or vinyl groups or as described, for example, in WO 2000/031148 (incorporated herein by reference in its entirety). It may be formed from monomers forming a [2 + 2] photo-added cyclization reaction as described in 2001/001143 or WO 2003/0014392, each of which is incorporated herein by reference in its entirety. Other suitable polymers are copolymers of SFA and SFA derivatized with bromo-acetamide groups (eg BRAPA), or copolymers of SFA and SFA derivatized with azido-acetamide groups.

The intermediate structure 34 may be a preformed gel material. The preformed gel material may be coated using spin coating, or dipping, or the flow of the gel under positive or negative pressure, or the technique set forth in US Pat. No. 9,012,022, which is incorporated herein by reference in its entirety. Dipping or dip coating may be a selective deposition technique depending on the surface 30 and the intermediate structure 34 used. By way of example, surface 30 may be dipped in preformed gel material 34, and gel material 34 may optionally be filled, coated, or deposited into well 31 (ie, gel material 34). Not deposited on the inter silver region 33), polishing (or other removal process) may not be necessary.

The preformed polymer or PAZAM can be coated on the surface 30 using, for example, spin coating, or dipping, or gel flow under positive or negative pressure, or the technique set forth in US Pat. No. 9,012,022. Desorption of the polymer or PAZAM can also occur via surface initiated atom transfer radical polymerization (SI-ATRP) to the silanized surface. In this example, the surface 30 may be pretreated with APTS (methoxy or ethoxy silane) to covalently link silicon to one or more oxygen atoms on the surface (without being intended to be maintained by the mechanism, Each silicon may be bonded to one, two or three oxygen atoms). This chemically treated surface is calcined to form an amine group monolayer. The amine group is then reacted with sulfo-HSAB to form an azido derivative. Of 1J / ㎝ ² to 30J / ㎝ ² UV activation at 21 ° C. by energy produces active nitrene species that can easily undergo various intercalation reactions with PAZAM.

Other examples for coating polymers or PAZAM on surface 30 are described in U.S. Patent Publication No. 2014/0200158, which is incorporated herein by reference in its entirety, and the ultraviolet light of PAZAM monomers to the amine-functional surface. UV) mediated linking, or thermal linking involving an active group (acryloyl chloride or other alkene or alkyne-containing molecule) by subsequent deposition of PAZAM and application of heat. In some examples, the surface 30 comprises azido-functionalized polymers such as PAZAM or azido-derivatized SFAs under conditions such as click chemistry to form covalent bonds between the modified surface and the polymer. It is modified with alkenyl or cycloalkenyl groups that can react with one.

The intermediate structure 34 may be a liquid that subsequently forms the gel material 34. An example of applying a liquid that subsequently forms gel material 34 is well 31 in liquid form with silane acrylamide and N- [5- (2-bromoacetyl) aminopentyl] acrylamide (BRAPA). It is a coating of an array of and allows the reagent to form a gel by polymerization on the surface. Coating of the array in this method can use the chemical reagents and procedures presented in US Patent Publication No. 2011/0059865.

The intermediate structure 34 may or may not be covalently connected to the surface 30 (in the well 31) or covalently to the surface 30. Covalent bonding of the polymer to the well 31 helps to maintain the intermediate structure 34 within the well 31 throughout the life of the surface 30 during various uses. However, as mentioned above and in many instances, the intermediate structure 34 need not be covalently bonded to the well 31. For example, silane free acrylamide, ie SFA, does not covalently attach to any portion of surface 30.

In an example of a method for using the surface 30, the amplification primer 36 is an intermediate structure 34 present in the well 31 (ie, in the replication of the plurality of nanofeatures 12) via any suitable method. ) May be bonded onto the substrate. In some examples, amplification primers include functional groups (eg, alkynyl or thiophosphate groups) that can react with functional groups in the intermediate structure 34 (eg, azido groups) to form covalent bonds.

To further illustrate the present disclosure, examples are provided herein. It is to be understood that these embodiments are provided for illustrative purposes and should not be construed as limiting the scope of the disclosure.

Example

Example 1

D4-tetra-ethyl triethoxysilane was used as an exemplary ASL material. D4-tetra-ethyl triethoxysilane is an octamethylcyclotetrasiloxane in which one methyl group at each silicon position is replaced by a (triethoxysilyl) ethyl- group. Fluorinated polymeric material was used as comparative ASL material. Exemplary ASL materials were incorporated into formulations containing about 5% by weight of material in tetrahydrofuran (THF).

Silicon masters each comprising a plurality of defined nano-sized features were coated with an ASL material and a comparative ASL material, respectively. The ASL material and the comparative ASL material were thermally cured and solvent washed.

The same type of work stamp resin formed from silicone acrylate monomers was spin coated on each coated silicon master and exposed to ultraviolet light (UV curing) to form a work stamp and a comparative work stamp. After one work stamp (first generation) or comparison work stamp was created, the work stamp or comparison work stamp was released from each coated silicon master, and the coated silicon master was added to the additional work stamp and the comparison work stamp (second generation, 3G, 4G, 5G, etc.)

Work stamps and comparative work stamps were used in nanoimprint lithography (NIL) inspection. Each work stamp was used to imprint 25 different samples (via NIL) and each compare work stamp was used to imprint 25 comparison samples (via NIL). The first imprint (Imp # 1) and the 25th imprint (Imp # 25) generated by using the first generation job stamp (Example # 1) and the fifth generation job stamp (Example # 2), respectively, surface roughness was determined by exposure to force microscopy (AFM). The first imprint (Imp # 1) and the 25th imprint (Imp # 25) generated using each first generation comparative work stamp (Comparative # 1) and fifth generation comparative work stamp (Comparative # 2) are also exposed to AFM. Surface roughness was determined. These results are shown in FIG. As shown, the surface roughness is formed of an exemplary work stamp (ie, formed from a silicon master coated with an ASL material) compared to an imprint formed of a comparative work stamp (ie, formed from a silicon master coated with a comparative ASL material). Lower for each imprint. In some examples, the surface roughness of the imprint generated from the work stamp as described herein is less than 100 nm, or less than 80 nm, or less than 60 nm or less than 50 nm or 40 (using the test method described herein). Less than nm, or less than 30 nm.

7A and 7B are 30 μm and 5 μm AFM images of a 25th imprint (Imp # 25) produced from a fifth generation work stamp produced from a silicon master coated with an exemplary ASL material, respectively. These images show that round wells and sharp well edges can be created even after the coated silicon master is used to form some work stamps, and even after the work stamps produced from the coated silicon master have been used for imprinting several times. It is present.

Exemplary ASL materials were also coated on two silicon masters (in a single ASL material deposition). The same type of work stamp resin formed from silicone acrylate monomers was spin coated on each of the coated silicon masters A and B and exposed to ultraviolet light (UV curing) to form a work stamp and a comparative work stamp. After one work stamp (1st generation A or B), the work stamp was released from each coated silicon master A or B and additional work stamps (2nd generation, 3rd generation, 4th generation, 5th generation, 50th generation) were created. Coated Silicon Masters A and B were used again. Fifty work stamps were generated and tested for A master, and then thirty work stamps were created and tested for B master.

Job stamps were used in nanoimprint lithography (NIL) inspection. Each working stamp was used to imprint 25 different samples (via NIL). Each 1st Generation Job Stamp (WS # 1), 5th Generation Job Stamp (WS # 5), 15th Generation Job Stamp (WS # 15), 20th Generation Job Stamp (WS # 20), 25th Generation Job Stamp (WS # 25) ), 30th Generation Job Stamp (WS # 30), 35th Generation Job Stamp (WS # 35), 40th Generation Job Stamp (WS # 40), 45th Generation Job Stamp (WS # 45), and 50th Generation Job Stamp (WS # 50) The surface roughness was determined by exposing the first imprint (Ima # 1) and the 25th imprint (Ima # 25) generated by using AFM.

These results are shown in FIG. 6, which shows the evolution of the imprint surface roughness (for first and twenty-fifth imprints) as a function of work stamp generation. For the first imprint created, the surface roughness is independent of the work stamp generation used. For subsequent imprints (eg Ima # 25), surface roughness was slightly increased by work stamp generation. Using WS # 50 formed from either coated silicon master A or B, imprints with low surface roughness (<100 nm) can still be produced. It is possible to produce 50 work stamps from one ASL coated master (if the ASL material is coated in a single deposition) and use all 50 to create an unusable imprint (e.g. There is a significant improvement in process capability as compared to similar processes using leaned polymeric materials.

Example 2

D4-tetra-ethyl triethoxysilane was used as an exemplary ASL material. Fluorinated polymeric material was used as comparative ASL material. ASL materials were incorporated into formulations containing about 5% by weight of material in tetrahydrofuran (THF).

Silicon masters each comprising a plurality of defined nano-sized features were coated with an ASL material and a comparative ASL material, respectively. The ASL material and the comparative ASL material were thermally cured and solvent washed. In some examples, the solvent is THF. In another example, the solvent solubilizes the uncured ASL material.

Different types of working stamp resins were used in this example. One working stamp resin was formed of silicone acrylate monomers. Another work stamp resin was a fluorinated work stamp material. The silicone acrylate working stamp resin was spin coated onto a silicone master coated with ASL material and then exposed to UV curing to form at least five generations of working stamps. A fifth generation was used in this example, referred to as job stamp example # 3. The silicone acrylate working stamp resin was spin coated onto a silicone master coated with a comparative ASL material and then exposed to UV curing to form at least five generations of the comparative working stamp. The fifth generation of these comparison work stamps was used in this example and is referred to as comparison work stamp # 3 (comparative example # 3). The fluorinated work stamp material was spin coated onto a silicon master coated with a comparative ASL material and then exposed to UV curing to form at least five generations of additional comparative work stamps. In this example a fifth generation of additional comparison work stamps was used and referred to as comparison work stamp # 4 (comparative example # 4).

Job Stamp # 3 and Comparative Job Stamps # 3 and # 4 were used in Nanoimprint Lithography (NIL) inspection. Each different work stamp was used to imprint 25 different samples (via NIL), and each comparison working stamp was used to imprint 25 different comparison samples (via NIL).

After 25 imprints, the formed silicon master coated with the comparative master stamp # 3 (ie, the fifth generation silicon acrylate task stamp resin formed of the comparative (i.e. fluorinated) ASL material) was coated with a scanning electron Microscopic (SEM) images (not shown) indicated that there were holes in the bottom of the printed wells. This particular combination of materials also suffered backwetting (ie, the fifth generation silicone acrylate working stamp resin is backwetting from a comparative (ie fluorinated) ASL material) and therefore cannot be used on automated tools.

8A and 8B are top down and cross-sectional SEM images of a twenty-fifth imprint formed from work stamp # 3. Imprints formed from silicone acrylate working stamp resins formed on silicon masters coated with ASL materials exhibit desirable levels of pattern accuracy and sharp, well defined edges. The surface roughnesses were relatively low R (5 mu m) = 2 nm and R (30 mu m) = 3 nm. 9A and 9B are top down and cross-sectional SEM images of a twenty-fifth imprint formed from comparative work stamp # 4. Imprints formed from fluorinated work stamp materials formed on silicon masters coated with comparative ASL materials exhibited desirable levels of pattern accuracy, but well rounded, surface roughness of relatively high R (5 μm) = 11 nm and R (30 mu m) = 12 nm. This data indicates that similar materials do not necessarily result in suitable imprints for work stamp resins and ASL materials (eg, silicon based work stamps formed on silicon based ASL materials or fluorinated work stamps formed from fluorinated ASL materials). Indicates. In fact, comparison job # 4 did not produce a suitable imprint.

Additional Notes

It is to be appreciated that all combinations of the aforementioned concepts, provided these concepts are not mutually inconsistent, are intended to be part of the subject matter of the invention disclosed herein. In particular, all combinations of the claimed subject matter presented at the end of this disclosure are assumed to be part of the subject matter of the invention disclosed herein. It is also to be appreciated that the terminology used explicitly herein, which may also appear in any disclosure incorporated by reference, should be in accordance with the meaning that most closely matches the specific concepts disclosed herein.

All publications, patents, and patent applications cited herein are hereby incorporated by reference in their entirety.

Reference throughout this specification to “an example”, “another example,“ an example ”, etc., includes certain elements (eg, features, structures, and / or features) described in connection with the example in at least one example described herein; In addition, it is understood that elements described with respect to any example may be combined in any suitable manner in the various examples, unless expressly indicated otherwise. Should be.

It is to be understood that the ranges provided herein include the stated range and any value or subrange within the stated range. For example, the range of about 5% to about 10% by weight includes explicitly quoted limits of about 5% to about 10% by weight as well as individual values such as about 5.2% by weight, about 6% by weight , About 7% by weight, and the like, and subranges such as about 5.5% to about 8% by weight, and the like. Furthermore, when “about” and / or “substantially” are used to describe a value, they are meant to include some variation (maximum +/− 10%) from the stated value.

While some examples have been described in detail, it should be understood that the disclosed examples may be modified. Accordingly, the foregoing description should be considered as non-limiting.

Claims (34)

As an imprinting device,
A silicon master comprising a plurality of defined nanofeatures; And
An anti-sticking layer for coating the silicon master, comprising an anti-sticking layer comprising molecules having a cyclosiloxane having at least one silane functional group. The method of claim 1, wherein the molecule is a cyclosiloxane, cyclotetrasiloxane, Cyclopentasiloxane, or a siloxane-cyclohexadiene, and the molecule is at least one unsubstituted ring substituted with a C _{1- 6} alkyl group, and at least substituted with an alkoxy silane a C _1-, the imprinting apparatus ₁₂ is substituted by an alkyl group. Article according to any one of the preceding claims, wherein the molecule comprises four unsubstituted C _{1- 6} alkyl group a, and a tri-alkoxysilane group, the imprinting unit substituted with _1- 4 C ₁₂ alkyl group which is substituted, each is substituted by the second term. The imprinting apparatus of claim 2 or 3, wherein the unsubstituted C _1-6 alkyl group is a methyl group. The imprinting apparatus according to any one of claims 2 to 4, wherein the C _1-12 alkyl group each substituted with the alkoxysilane group is an ethyl or propyl group. The imprinting apparatus of claim 5, wherein the C _1-12 alkyl group each substituted with the alkoxysilane group is an ethyl group. The imprinting apparatus according to claim 2, wherein the alkoxysilane or trialkoxysilane group is trimethoxysilane or triethoxysilane. The imprinting apparatus of claim 7, wherein the alkoxysilane or trialkoxysilane group is triethoxysilane. The imprinting apparatus of claim 1, wherein the cyclosiloxane is selected from the group consisting of cyclotetrasiloxane and cyclohexasiloxane. The imprinting apparatus of claim 9, wherein the silane functional group is an alkyl alkoxysilane. The imprinting apparatus of claim 10, wherein the alkyl alkoxysilane is ethyl triethoxysilane. The method according to any one of claims 1 to 11, wherein the molecule is

Phosphorus, imprinting device. The imprinting apparatus of claim 1, wherein the anti-stick layer comprises a mixture of the molecule and oligomers of the molecule in pure form. The imprinting apparatus of claim 1, further comprising a silicon-based work stamp in contact with the anti-stick layer on the silicon master. The imprinting apparatus of claim 14, wherein the silicone based work stamp comprises a polymerized silicone acrylate monomer. 16. An imprinting apparatus according to claim 14 or 15, further comprising a back plate in contact with the work stamp. The imprinting device of claim 1, wherein the molecule excludes fluorine. As a method,
Forming a master mold,
Depositing a formulation on a silicon master comprising a plurality of defined nanofeatures, wherein the formulation comprises solvent and molecules having a cyclosiloxane having at least one silane functional group; And
Forming an anti-stick layer on the silicon master by curing the formulation, wherein the anti-stick layer comprises the molecule, forming the anti-stick layer
Thereby forming the master mold;
Depositing a silicon based work stamp material on the anti-stick layer of the master mold;
Curing the silicone-based work stamp material to form a work stamp comprising the plurality of nanofeatures negative replicas; And
Releasing the work stamp from the master mold. The method of claim 18,
The solvent has a boiling point of less than about 70 ° C .; And
The molecule is present in the formulation in an amount of at least about 5% by weight. The method of claim 18, wherein the solvent is tetrahydrofuran or toluene. 21. The method of any of claims 18-20, wherein depositing the formulation and depositing the silicon-based work stamp material each comprise spin coating. 22. The method of any one of claims 18 to 21, wherein the silicone based work stamp material comprises a silicone acrylate monomer. 23. The method of any one of claims 18 to 22, wherein the molecule is present in the formulation in an amount ranging from about 5% to about 10% by weight. The method of claim 18, wherein the released work stamp is at least substantially free of the molecule. The method according to any one of claims 18 to 24, wherein the molecule is

That's how. The method of claim 18, wherein the molecule excludes fluorine. 27. The method of any one of claims 18 to 26, wherein releasing the work stamp provides a released master mold having the anti-stick layer, wherein the method comprises:
Depositing a second silicon based work stamp material on the anti-stick layer of the released master mold;
Curing the second silicon-based work stamp material to form a second work stamp comprising the plurality of nanofeatures negative copies; And
Releasing the second work stamp from the master mold. 28. The method of claim 27, further comprising cleaning the released master mold prior to the deposition of the second silicon-based work stamp material. As a method of using a job stamp, the job stamp,
Forming a master mold,
Depositing a formulation on a silicon master comprising a plurality of defined nanofeatures, the formulation comprising a solvent and a molecule having a cyclosiloxane having at least one silane functional group; And
Forming an anti-stick layer on the silicon master by curing the formulation, wherein the anti-stick layer comprises the molecule, forming the anti-stick layer
Thereby forming the master mold;
Depositing a silicon based work stamp material on the anti-stick layer of the master mold;
Curing the silicon-based work stamp material to form a work stamp comprising the plurality of nanofeatures negative copies; And
Ejecting the work stamp from the master mold
Formed by
The method using the job stamp,
Imprinting the working stamp on an imprint lithography resin on a support; And
Forming a sequencing surface having a plurality of replicas of the nanofeatures defined by curing the resin. The method of claim 29, wherein the sequencing surface is at least substantially free of the molecule. 31. The method of claim 29 or 30, further comprising conjugating amplification primers on intermediate structures present in the replica of the plurality of nanofeatures. The method of claim 31, wherein the intermediate structure is a polymer coating comprising repeat units of formula (I)

During the formula:
R ¹ is H or optionally substituted alkyl;
R ^A is azido, optionally substituted amino, optionally substituted alkenyl, optionally substituted hydrazone, optionally substituted hydrazine, carboxyl, hydroxy, optionally substituted tetrazole, optionally substituted tetra Selected from the group consisting of gin, nitrile oxide, nitrone and thiol;
R ⁵ is selected from the group consisting of H and optionally substituted alkyl;
Each — (CH ₂ ) _p — may be optionally substituted;
p is an integer ranging from 1 to 50;
n is an integer ranging from 1 to 50,000; And
m is an integer ranging from 1 to 100,000. 33. The method of any of claims 29 to 32, wherein the molecule is

How to be. 33. The method of any one of claims 29-32, wherein the molecule excludes fluorine.

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